KR850001041B1 - Process for preparing xanthene-yl esters of phor-sphoric and phosphonic acids - Google Patents

Abstract

Xanthenone-yl esters of phosphoric acid and phosphoric acids of formula (I) are new. In (1), R1 and R2 are each lower alkyl or cyano; k and m are integers of 0-1; Q and Y are O or S; R3 is lower alkyl or a gp. of formula (II) ; R4 is lower alkyl, lower alkoxy or a gp. of formula (III); R5 is halogen, lower alkyl or cyano; n is 0-3; R6 is lower haloalkyl, nitro, or cyano; P is 0-3; and A and B are each O or S, provided that if R4 is lower alkoxy then one of A or B is S. An insecticidal compd. contg. (I) is claimed.

Description

Process for preparing xanthenone-yl ester of phosphoric acid and phosphonic acid

The present invention relates to a process for the preparation of novel compounds having the general formula (I) which is useful as a pesticide.

(여기서 R⁵는 할로겐, 알킬, 할로알킬, 니트로 및 시아노로 구성되어 있는 그룹으로부터 선택되며 : 또한 n은 0 내지 3임)으로 구성되어 있는 그룹으로부터 선택되며 : R⁴는 알킬, 알콕시, 알킬티오, 아미노, 알킬아미노, 디 알킬아미노 및 구조식

(여기서 R⁶는 할로겐, 알킬, 할로알킬, 니트로 및 시아노로 구성되어 있는 그룹으로부터 선택되며 : 또한 P는 0 내지 3임)으로 구성되어 있는 그룹으로 부터 선택되며 : 및 A 및 B는 각각 산소 및 황으로 구성되어 있는 그룹으로부터 선택된다. ( 단, R⁴가 알콕시인 경우, A와 B중 하나는 황이어야만 한다). 이들 화합물은 살충제로써 유용하다.Wherein R ¹ and R ² are each selected from the group consisting of halogen, alkyl, haloalkyl, nitro, alkylsulfinyl, alkylsulfonyl and cyano: K and m are 0 to 3 and Q is oxygen And sulfur; Y is selected from the group consisting of oxygen and sulfur: R ³ is alkyl and structural formula

Wherein R ⁵ is selected from the group consisting of halogen, alkyl, haloalkyl, nitro and cyano; and n is 0-3; and R ⁴ is alkyl, alkoxy, alkylthio , Amino, alkylamino, dialkylamino and structural formulas

Wherein R ⁶ is selected from the group consisting of halogen, alkyl, haloalkyl, nitro and cyano; and P is 0-3; and A and B are each oxygen and It is selected from the group consisting of sulfur. Provided that when R ⁴ is alkoxy one of A and B must be sulfur. These compounds are useful as insecticides.

(여기서 R⁵은 할로겐, 저급알킬, 저급할로알킬, 니트로 및 시아노이며, n은 0 내지 3임)으로 구성되어 있는 그룹으로부터 선택되며 : R⁴는 저급알킬, 저급알콕시, 저급알킬티오, 아미노 저급알킬티오, 디(저급알킬)아미노 및 구조식

(여기서 R⁶는 할로겐, 저급알킬, 저급할로알킬, 니트로 및 시아노로 구성되어 있는 그룹으로부터 선택되며, P는 0 내지 3임)으로 구성되어 있는 그룹으로부터 선택되며 : 또한 A와 B는 각각 산소와 황으로 구성되어 있는 그룹으로부터 선택된다. (단, R⁴가 알콕시인 경우 A와 B중 어느 하나는 황이어야만 된다) 본 명세서에서 사용된 "저급"이란 말은 탄소원자 6 이하의 직쇄 또는 분지쇄탄소를 의미한다.In a preferred embodiment of the invention, R ¹ and R ² are each selected from the group consisting of halogen, lower alkyl, lower haloalkyl, nitro lower alkylsulfinyl, ziralkylsulfonyl and cyanolol: K and m are 0-3: Q is selected from the group consisting of oxygen and sulfur, and: R ³ is lower alkyl and the following structural formula

Wherein R ⁵ is halogen, lower alkyl, lower haloalkyl, nitro and cyano, n is from 0 to 3; and R ⁴ is lower alkyl, lower alkoxy, lower alkylthio, Amino lower alkylthio, di (lower alkyl) amino and structural formula

Wherein R ⁶ is selected from the group consisting of halogen, lower alkyl, lower haloalkyl, nitro and cyano, and P is 0-3; and A and B are each oxygen It is selected from the group consisting of and sulfur. Provided that any of A and B must be sulfur when R ⁴ is alkoxy. As used herein, the term "lower" means a straight or branched carbon having up to 6 carbon atoms.

The compound according to the present invention can be prepared by reacting a compound of formula (II) with a compound of formula (III).

In the general formula, R ¹ , R ² , R ³ , R ⁴ , K, m, Q, Y, A and B are as defined above.

The reaction according to the present invention can be effectively carried out by dissolving or slurrying a compound of formula (II) with an acid acceptor such as potassium carbonate or triethylamine in an inert reaction medium such as acetonitrile or tetrahydrofuran.

To the solution / slurry is added a compound of formula III with stirring at a temperature of about 0 ° C to 40 ° C. The reaction mixture can be stirred for several hours after completion of the reaction, the acid acceptor salts are removed and the desired product is isolated and purified by commercial techniques.

The compound of formula (II) wherein Y is oxygen can be prepared by the following scheme.

In the above formula,

R ¹ , R ² , K, m and Q are as defined above. The alkoxy group of the compound of formula (V) may be any lower alkoxy, but methoxy is preferred.

In addition, the compound of formula (V) must have at least one hydrogen in the ortho position relative to the —QH group. Since the position of the hydroxyl group of the compound of formula (II) is determined by the position of the alkoxy group which is closely related to the -QH group of the compound of formula (V), this compound is obtained in order to obtain a compound of formula (II) having a desired structure. Is selected. However, when the ortho at both positions for the —QH group of the compound of formula (V) is hydrogen, a mixture of the position isomers of the compound of formula (VII) and the position isomers of the compound of formula (II) is produced.

These isomers can be separated and the desired isomers of the general formula (II) compounds are isolated by known methods such as fractional stabilization, differential solubilization, high performance liquid chromatography and the like.

In carrying out the reaction continuously, the compounds of formulas (IV) and (V) are dissolved in an inert reaction medium such as 1-pentanol and the copper catalyst (preferably as a paper by PHGore and GK Hughes Prepared by the method described in Chemical Society 1615 (1959), wherein potassium carbonate is added to an inert reaction match such as copper metal precipitated from copper sulfate solution by zinc powder and the mixture is stirred and then refluxed at solvent Heat for about 0.5 to about 8 hours.

When a compound of the general formula (VI), which is a non-cyclized concentrated antibiotic, is treated with concentrated sulfuric acid, a cyclization reaction occurs to give a compound of the general formula (VII). When using an inert reaction medium such as acetyl chloride, the reaction is carried out at room temperature or slightly elevated temperature for about 0.5 to 2 hours.

Compounds of formula (II) are generally known and are also prepared by treating compounds of formula (VII) with anhydrous aluminum chloride for about 2-4 hours at a temperature of 80 ° C. to 90 ° C. in an inert reaction medium such as toluene. can do.

Hydrochloric acid with a concentration of about 6N is added and the mixture is stirred at a temperature of 80 ° C to 90 ° C for about 2 to 4 hours. The compound of formula (II) wherein Y is sulfur is prepared by the following scheme.

In the above formula,

R ¹ , R ² , K, m and Q are as defined above.

The compound of formula (VII) is mixed with P ₂ S ₅ without diluent and heated at a temperature of about 130 ° C. to 140 ° C. for about 0.5 to 4 hours. Unreacted P ₂ S ₅ was removed by hydrolysis with water; The compound of the general chamber IX is recrystallized using, for example, ethanol.

Compounds of formula (X) were treated with anhydrous aluminum chloride as described above for preparing compounds of formula (II) from compounds of formula (VII), The compound of X) can be prepared.

Examples of compounds of general formula (III) suitable for preparing the compounds of the present invention include 0-ethyl S-propyl phosphorochloridoriooleate: 0-ethyl S-propyl phosphorochloridothiorothiolate: 0- ( 2,4-dicyanophenyl) S-propyl phosphorochloridothiolate: 0- (3,4,5-trichlorophenyl) S-propyl phosphorochloridothiolate: S-ethyl S-propyl phosphorochloro Lydothiolate: S-Butyl S-pentyl phosphorochloridothiothiolothionethiate: S-pentylethyl phosphonochloridothiolane S- (3-nitropinyl) (3-chlorophenyl) phosphonoclo Lydothiolothionate: 0- (2,3-dimethylphenyl) S-butyl phosphorochloridothiolate: 0-ethyl 0-butyl phosphorochloridothionate: 0- (4-chloro-5-methylphenyl) 0-propyl phosphorochloridothionate: 0-ethyl S-propyl phosphorochloridothiolothione Yate: 0-ethyl ethyl phosphonochloridothiolate: 0-ethyl N, N-dimethyl phosphorimidochloridate: S-propyl N, N-diethylphosphoramidochloridothiolate: S-pentyl N, N-dinucleosilphosphoramidochloridothiolothionate: 0-butyl N-butylphosphoramidochlorate: S-hexyl phosphoramidochloridothiolothionate: 0-butyl N- Butylphosphoramidochlorate: S-hexyl phosphoramidochloridothiolate and the like.

Examples of compounds of the general formula (IV) suitable for preparing the compounds of the present invention include 2-chlorobenzoic acid: 2-chloro-3-cyanobenzoic acid: 2-chloro-4,5-dimethylbenzoic acid: 2-3,5- Trichlorobenzoic acid: 2-chloro-4- (trifluoro-methyl) benzoic acid: 2-chloro-3-ethylsulfinylbenzoic acid: 2,3,4-trichloro-sulfonylbenzoic acid: 2,4-dichloro-3 -Methyl-5-cyanobenzoic acid: 2-chloro-5-nitrobenzoic acid and the like.

Examples of compounds of the general formula (V) suitable for preparing the compounds of the present invention include 2-methoxyphenol: 2-methoxy-3,4-dichlorophenol: 2-methoxy-4,5-dimethylphenol: 2- Methoxy-5-nitrophenol: 2-methoxy-3- (trifluoromethyl) phenol: 2-methoxy-4-ethylsulfinylphenol: 2-methoxy-3,5-dicyanophenol: 2- Methoxy-3,4,5-tribromophenyl: 2-methoxy-4-ethylsulfonylphenol: 2-methoxy-4-cyanobenzenethiol: 2-methoxy-3,4, -dinitro Benzene Thiol: 2-methoxy-3-trichloromethyl-4-ethylbenzenethiol: 2-methoxy-4-ethylsulfinylbenzenethiol: 2-methoxy-4-methyl-5-propylsulfonylbenzenethiol: 2-methoxy-3,4-dichlorobenzenethiol: 3-methoxy-4-bromophenol: 3-methoxy-5,6-dinitrophenol: 3-methoxy-4,5-dicyanophenol: 3-methoxy-4-butylsulfinylphenol: 3-methoxy-5-ethyl-6- (trifluoromethyl): 3-methoxy-4-propylsulfonyl-phenol: 2,5-dibromo 3-methoxyphenol: 3-methoxyphenol-2,4- Dichloro-3-methoxybenzenethiol: 2,5-dicyano-3-methoxybenzenethiol: 3-methoxy-5-butylsulfonylbenzenethiol: 3-methoxy-4,5,6-trichloro- Benzenethiol: 2-trifluoromethyl-3-methoxybenzenethiol: 3-methoxy-5-butylsulfinylbenzenethiol: 4-methoxyphenol: 2-chloro-3-ethyl-4-methoxyphenol: 3 -Nitro-4-methoxyphenol: 2- (1-ethylpropyl) -3-cyano-4-methoxyphenol: 2,3-dibutyl-4-methoxyphenol: 3-ethylsulfonyl-4- Methoxyphenol: 4-methoxy-5-butylsulfonyl-tenol: 4-methoxy-5-trifluoromethylphenol: 2,3, -dichloro-5- (2-ethylbutylbenzenethiol: 3-sia No-4-methoxybenzenethiol: 2-ethyl-3- (trifluoromethyl) benzenethiol: 3-nitro-4-methoxybenzenethiol: 2-propylsulfinyl-4-methoxybenzenethiol: 3-bro Mother-4-methoxy-5-ethylsulfonylbenzenethiol, and the like.

Example 1

Preparation of 0,0-dienyl 0- (xanthene-9-one-2-yl) phosphorothionate

2-hydroxy xanthene-9-one (1.0 g: 0.0047 mole), 0,0-dimethyl-phosphorochloridothioneine (0.89 g: 0.0049 mole), acetonitrile (25 ml) and potassium carbonate (1.94 g : 0.0047 mole) is filled in a glass reaction vessel equipped with a stirrer and a thermometer, and then the reaction mixture is stirred at a temperature of about 40 ° C. to 45 ° C. for about 16 hours, and the resulting precipitate is filtered, washed with acetonitrile, and filtered. Add to water.

An acetonitrile solution mixed with an equal amount of acetonitrile is added, silica gel (2 g) is added, and the slurry is stirred at room temperature for about 1 hour 30 minutes. The silica gel was filtered, the filtrate was treated with activated charcoal and then refiltered and the solvent was removed by rotary evaporator (70 ° C., 1/5 mmHg) to give brown oil.

The obtained oil is dissolved in a 1/1 mixture of chloroform / cyclohexane (16 ml), silica gel (2 g) is added and stirred at room temperature for 2 hours 30 minutes.

The silica gel is filtered off, washed with toluene, and the washing solution is mixed with the filtrate. The solvent is then removed from the filtrate to afford the desired product 0,0-diethyl 0- (xanthene-9-one-2-yl) phosphorothionate.

Elemental Analysis:

Theoretic Value: C = 56.04%: H = 4.70%: P = 8.50%

Found: C = 55.76%: H = 4.73%: P = 8.5%

Example 2

Preparation of 1-ethyl 0- (xanthene-9-one-2-yl) S-propyl phosphorothiolate

2-hydroxyxanthene-9-one (1.4 g: 0.0066 mol) was added to methylene chloride (10 ml) to make a slurry and 0-ethyl S-propyl force in methylene chloride contained in a glass reaction vessel with a stirrer and a thermometer. To the polochloridothiolate solution dropwise dropwise at about 0 ° C. for about 5 minutes, then the reaction mixture is cooled to about −65 ° C. and triethylamine (0.67 g) in methylene chloride (2 ml) is added.

The reaction mixture is stirred at a temperature of about 10 ° C. for about 2 hours, left at room temperature for about 16 hours, the mixture is diluted with an equal amount of methylene chloride and the solution is washed with cold water (about 3-30 ml) and then separated (Phase Separation paper), treated with activated charcoal and filtered. The solvent is removed with a rotary evaporator (70 ° C., 15 mm Hg) to give a condensed brown oil.

The reason is added to 5 parts by weight of diisopropyl ether and the mixture is heated to reflux, then cooled and filtered.

The ether is removed with a rotary evaporator to yield a yellow oil which is then dissolved in a solvent consisting of 60 parts by weight of chloroform and 40 parts by weight of cyclohexane. Silica gel (2 g) is added to this solution and the mixture is stirred at room temperature for about 1 hour and then filtered.

The silica gel is washed with 60/40 parts by weight of chloroform / cyclohexane (1.0 ml) and the wash is mixed with the filtrate. The solvent is partially removed by rotary evaporator, and then the concentrate is chromatographed on silica gel column using 40/60 parts by weight of ethyl acetate / cyclohexane as diluent.

Fractions containing the desired product are identified by NMR analysis. This fraction is mixed and the solvent is removed with a rotary evaporator to give the desired product 0-ethyl-0- (xanthene-9-one-2-yl) S-propylphosphothiolate of clear yellow oil which is recrystallized upon standing. do.

Elemental analysis

Theoretic Value: C = 57.13%: H = 5.06%: P = 8.19%

Found: C = 57.13%: H = 5.10%: P = 7.75%

Example 3

Preparation of 0-phenyl 0- (xanthene-9-one-2-yl) S-propyl phosphorothiolate

2-Hydroxyxanth-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and 0-phenyl S in acetonitrile (6 ml). Propyl phosphochloridothiolate (0.01 mol) is added dropwise dropwise with stirring at room temperature. The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mmHg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml).

The solution is then slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. The solvent is removed from the filtrate using a rotary evaporator to afford the desired product 0-phenyl 0- (xanthene-9-one-2-yl) S-propyl phosphorothiolate.

Example 4

Preparation of 0- (xanthene-9-on-2-yl) S-nitrophenyl S-propyl phosphorodithiolate

2-Hydroxyxanth-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) are filled in a glass reaction vessel equipped with a stirrer and a thermometer and S- (4 in acetonitrile (6 ml). Nitrophenyl) S-propyl phosphorus Chloridodithiolate (0.01 mol) is added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered. The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mmHg_) and the nonvolatile residue is redissolved in 1/1 parts by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with a silica gel (2 g) for about 2 hours at room temperature and then filtered.

The solvent is removed from the filtrate using a rotary evaporator to afford the desired product 0- (xanthene-9-one-2-yl) S- (nitrophenyl) S-propyl phosphorothiolate.

Example 5

Preparation of 0-ethyl 0- (xanthene-9-thion-2-yl) S-propyl phosphorothioolothionate

2-Hydroxyxanthene-9-thione (1.97 g: 0.009 mol) and acetonitrile (120 ml) were filled in a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, and xanthenthion was added to this solution while heating. After refluxing for a period of time, the solution was cooled to room temperature, treated with activated charcoal, filtered continuously and filled in a glass reaction vessel with a stirrer and thermometer. Potassium carbohydrate (1.2 g) and 0-ethyl S-propyl phosphorochloridothiolothionate (1.74 g) are added to the reaction vessel and the mixture is stirred for about 24 hours.

The reaction mixture is then warmed to about 50 ° C. and further stirred for about 7 hours.

The reaction mixture is filtered and the solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) to yield an oil.

This oil is dissolved in 6.5 parts by weight of chloroform and 93.5 parts by weight of cyclohexane (40 ml of solvent): silica gel (4 g) is added and the mixture is stirred at room temperature for about 2.5 hours.

The solution is filtered and the filtrate is treated with activated charcoal and refiltered. The solvent is removed with a rotary evaporator to afford the desired product 0-ethyl 0- (xanthene-9-thion-2-yl) S-propyl phosphorothioolothionate.

Elemental Analysis:

Theoretic Value: C = 52.67: H = 4.66: P = 7.55

Found: C = 52.25: H = 4.68: P = 7.37

Example 6

Production method of 0- (xanthene-9-thione-2-) S-ethylphenylphosphonothiolate

2-Hydroxyxanthene-9-thione (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and S-ethylphenyl in acetonitrile (6 ml). Phosphonochloridothiolate (0.01 mol) is added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mmHg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. The solvent is removed from the filtrates using a rotary evaporator to give the desired product 0- (xanthene-9-thion-2-yl) S-ethyl phenylphosphonothiolate.

Example 7

Preparation of 0-ethyl 0- (xanthene-9-thion-2-yl) S-propyl phosphorothiolate

2-Hydroxyxanth-9-thione (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel with a stirrer and a thermometer, and 0-ethyl in acetonitrile (6 ml). S-propyl phosphorochloridothiolate (0.01 ml) is added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg).

The nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane. The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered.

The solvent is removed from the filtrate using a rotary evaporator to afford the desired product 0-ethyl 0- (xanthene-9-thion-2-yl) S-propyl phosphorothiolate.

Example 8

Preparation of 0-ethyl 0- (xanthene-9-one-3-yl) S-propyl phosphorothiothionate

3-hydroxyxanthene-9-one (1.48 g: 0.007 mole) and acetonitrile (20 ml) were charged in a glass reaction vessel equipped with a stirrer and a thermometer, and the mixture was mixed with potassium carbonate (0.97 g, 0.007 mole). A solution of 0-ethyl S-propyl phosphorochlorido thiolothionate (1.41 g: 0.007 mol) in acetonitrile is added at room temperature.

The reaction mixture is stirred at a temperature of about 50 ° C. for about 54 hours and the reaction mixture is cooled to room temperature and filtered. The filtered solid agent is washed with acetonitrile (10 ml) and the washing solution is mixed with the filtrate.

The mixed filtrate / wash solution is concentrated by rotary evaporator to give a tan oil. This oil is dissolved in acetone (5 ml) and cyclohexane (95 ml) is added followed by 5 g of silica gel.

The mixture is stirred at room temperature for 1 hour, filtered and the silica gel is washed with 5/95 parts by weight of acetone / cyclohexane and the wash is mixed with the filtrate.

The solvent was removed from the mixed filtrate / wash using a rotary evaporator to yield 0-ethyl 0- (xanthene-9-one-3-yl) S-propyl phosphorothioolothionate, the desired product as a yellow oil. do.

Elemental Analysis:

Theoretic Value: C = 54.86%: H = 4.85%: P = 7.85%

Found: C = 55.57%: H = 4.99%: P = 7.41%

Example 9

Preparation of 0-ethyl 0- (xanthene-9-one-3-yl) S- (3,5-dichlorophenyl) phosphorothiol thionate

3-Hydroxyxanthene-9-one (0.01 mol) was filled in a glass reaction vessel equipped with a stirrer and a thermometer and in acetonitrile (6 ml) with 0-ethyl S- (3,5-dichlorophenyl) phosphorothiol. Thionate (0.01 mol) is added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml). The solution is slurried at room temperature with silica gel (2 g) for about 2 hours and then filtered.

The solvent was removed using a rotary evaporator to remove the solvent from the filtrate, thereby yielding the desired product 0-ethyl 0- (xanthene-9-one-3-yl) S- (3,5-dichlorophenyl) phosphorothiolothio Obtain the nate.

Example 10

Preparation of 0- (xanthene-9-one-4-yl) S-phenyl phenylphosphonothiolothionate

4-Hydroxyxanth-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and S-phenyl phenyl in acetonitrile (6 ml). The phosphonochloridothiolothionate is added dropwise dropwise while stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered. The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. The solvent is removed from the filtrate using a rotary evaporator to afford the desired product 0- (xanthene-9-one-4-yl) S-phenyl phenylphosphonothionate.

Example 11

0-ethyl 0- (xanthene-9-one-4-yl)

(Preparation of 2,4,6-trichlorophenyl (phosphonate:

4-hydroxyxanthene-9-one (0.01 mol), acetonitrile 25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and 0-ethyl (2 ml) in acetonitrile (6 ml). , 4,6-trichlorofinyl) phosphonochlorate (0.01 mol) was added dropwise dropwise with stirring at room temperature, then cooled to room temperature and filtered.

Solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mHg) and the nonvolatile residue is redissolved with 1/1 parts by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. Using a rotary evaporator, the solvent was removed from the filtrate to afford the desired product 0-ethyl 0- (xanthene-9-one-4-yl) (2,4,6-trichlorophenyl) phosphonate do.

Example 12

0-ethyl 0- (3,6-dimethylxanthene-9-one-2-yl)

Preparation of S-propyl phosphorothiolothionate:

2-hydroxy-3,6-dimethyl xanthene-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and acetonitrile (6 ml). 0-ethyl S-propyl phosphorochloridothiolothionate (0.01 mol) was added dropwise dropwise with stirring at room temperature, and then the reaction mixture was stirred at a temperature of about 35 ° C to 50 ° C for about 48 hours. Then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) and the nonvolatile residue is redissolved with 1/1 parts by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. Using a rotary evaporator, the solvent was removed from the filter and then the desired product, 0-ethyl0- (3,6-dimethylxanthene-9-one-2-yl) S-propyl phosphorothioolothionate, was obtained. do.

Example 13

Preparation of 0- (3,6-dimethylxanthene-9-one-2-yl) S-ethyl (2,6-dicyanophenyl) phosphonothiolothionate:

2-hydroxy-3,6-dimethylxanthene-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and acetonitrile (6 ml). ), S-ethyl (2,6-dicyanophenyl) phosphonochlorido thiolothionate (0.01 mol) is added dropwise dropwise while stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg). The nonvolatile residue is redissolved in 1/1 parts by weight of chloroform / cyclohexane (25 ml) and then the solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered.

Removal of the filtrate using a rotary evaporator yielded the desired product 0- (3,6-dimethylxanthene-9-one-2-yl) S-ethyl (2,6-dicyanophenyl) phosphonothiolothio Obtain the nate.

Example 14

0-hexyl 0- (3-nitroxanthene-9-one-4-yl)

Preparation of S- (2-methyl-4-bromophenyl) phosphorothiorothiolate:

3-nitro-4-hydroxyxanthene-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) are filled in a glass reaction vessel with a stirrer and a thermometer and acetonitrile (6 ml). 0-hexyl S- (2-methyl-4-bromophenyl) phosphorchloridothiolothionate (0.01 mol) is added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg). The nonvolatile residue is redissolved in 1/1 parts by weight of chloroform / cyclohexane (25 mL) and then the solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered.

The solvent was removed from the filtrate using a rotary evaporator and the desired product 0-hexyl 0- (3-nitroxanthen-9-one-4-yl) S- (2-methyl-4-bromophenyl) phosph Porothiolothionate is obtained.

Example 15

Preparation of 0- (3-nitroxanthene-9-one-4-yl) S-ethyl (4-trifluoromethylphenyl) phosphonothiolothionate:

3-nitro-4-hydroxanthene-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and acetonitrile (6 ml). S-ethyl (4-trifluoromethylphenyl) phosphonochloridothiolothionate (0.01 mol) in water was added dropwise dropwise while stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. The solvent was removed from the filtrate using a rotary evaporator and the desired product 0- (3-nitroxanthene-9-one-4-yl) S-ethyl (4-trifluoromethyl) phosphonothiolothionate To obtain.

Example 16

Preparation of 0-ethyl 0- (4-cyanoxanthene-9-one-3-yl) 4-chlorophenyl phosphonothionate:

1-hydroxy-4-nitro-6-cyanoxanthene-9-one (0.01 mol), acetonitrile (25 ml) and potassium carbonate (0.01 mol) are filled in a glass reaction vessel with a stirrer and a thermometer and 0-ethyl (4-chlorophenyl) phosphonochloridothionate is added dropwise in nitrile (6 mL) with stirring at room temperature.

The reaction mixture is stirred at a temperature of about 35 ° C. to 50 ° C. for about 48 hours, then cooled to room temperature and filtered.

The solvent is removed from the filtrate using a rotary evaporator (70 ° C., 15 mm Hg) and the nonvolatile residue is redissolved in 1/1 part by weight of chloroform / cyclohexane (25 ml).

The solution is slurried with silica gel (2 g) at room temperature for about 2 hours and filtered. The solvent was removed from the filtrate using a rotary evaporator to afford the desired product 0-ethyl 0- (4-nitro-6-cyanoxanthene-9-one-1-yl) 4-chlorophenylphosphonothioate. do.

Example 17

Preparation of 0-ethyl 0-thioxanthene-9-one-2-yl) S-propyl phosphorothiolothionate:

2-hydroxythioxanthene-9-one (2.28 g: 0.01 mol), acetonitrile (60 ml) and potassium carbonate (1.38 g, 0.01 mol) were filled in a glass reaction vessel equipped with a stirrer and a thermometer and acetonitrile 0-ethyl S-propyl phosphorochloridothiolothionate (2.8 g: 0.01 mol) in (3 mL) was added dropwise dropwise with stirring at room temperature.

The reaction mixture is stirred at room temperature for about 30 hours. After completion of stirring, the reaction mixture was filtered, the solvent was removed from the filtrate using a rotary evaporator, and the residue was subjected to column chromatography analysis using a mixture of 25/75 parts by weight of ethyl acetate, cyclohexane, and silica gel. The eluate is removed from the solvent to afford the desired product, oily 0-ethyl 0- (thioxanthene-9-one-2-yl) S-propyl phosphorothioolothionate.

Example 18

Preparation of 0-ethyl 0- (thioxanthene-9-one-2-yl) S-propyl phosphorothiolate:

2-hydroxythioxanthene-9-one (2 g: 0.009 mol), toluene (25 ml) tetrahydrofuran (26 ml) and triethylamine (0.89 g) were filled in a reaction vessel with a half-crosslinker and a thermometer. The mixture was cooled to 0 ° C. and 0-ethyl S-propyl phosphorochloridothiolate (0.009 mol) dissolved in toluene (16 mL) was added dropwise dropwise with stirring. After dropping, the mixture was left at room temperature overnight, and then the mixture was filtered. The solvent is removed and the residue is subjected to column chromatography analysis using 40/60 parts by weight of ethyl acetate cyclohexane mixture.

The eluate is removed from the solvent to give the oily product 0-ethyl 0- (thioxanthene-9-one-2-yl) S-propyl phosphorothiolate. If left to stand, it solidifies and becomes a solid having a melting point of 57 to 60 ° C.

Additional compounds in the context of the present invention that can be prepared according to the methods of the above-described examples are 0-ethyl 0- (5-trifluoromethylxanthene-9-one-2-yl) S-propyl phosphorothiol Rothionate: 0- (2-Chlorophenyl) 0- (7-ethylsulfonyl xanthen-9-one-2-yl) S-propyl phosphorothiolothionate: 0, 0-dipropyl 0- ( 6-Butylsulfinylxanthene-9-one-2-yl) phosphorothionate: 0-ethyl 0- (2-chloro-7-nitroxanthene-9-one-4-yl) S-propyl phosphorothiol Rothionate: 0- (3-nitrophenyl) 0- (2-chloro-6-nitro-7-ethylxanthene-9-one-4-yl) S-propyl phosphorothiolothionate: 0-ethyl 0- (3-Chloroxanthene-9-one-2-yl) S-propyl phosphorothiolothionate: S-ethyl 0- (xanthene-9-thione-2-yl) S-propyl phosphorothiol Rothionate: 0-ethyl 0- (3-chloroxanthene-9-thion-2-yl) S-propyl phosphorothioolothionate: 0- (3, 4-dimethyl-7-cyanok Ten-9-one-1-yl (S-pentyl S-hexyl fosoprothiolothionate: 0-ethyl 0- (4-ethylsulfonyl-8-ethylxanthene-9-one-2-yl) S-propyl phosphorothiolothionate: 0-hexyl 0- (1, 4, 6, 7-tetramethylxanthene-9-one-3-yl) S-butyl phosphorothiolate: 0- (2, 7-Dicyanoxanthene-9-one-4-yl) S-ethyl phenylphosphonothioolothionate: 0-ethyl 0- (2-nitro-6, 7-dichloroxanthene-9-one-2- I) S-propyl phosphorothiolothionate: 0- (1,4-dimethyl-5,8-dinitroxanthene-9-one-3-yl) S-ethyl S-propyl phosphorothiolothionate : 0- (6,7-detetylxanthene-9-thion-2-yl) S-ethyl S-propyl phosphorodithiolothionate: 0- (4-nitro-5-cyano-6-chloro Santen-9-thione-1-yl) S-butyl S-pentyl phosphorodithiolothionate: 0-ethyl 0- (1,4-dipropyl-6, 7-dichloroxanthene-9-thione-2 -Yl) S-propyl phosphorothiolothionate: 0-methyl-0- (4-cyano-6, 7-dichloroxanthene-9-thiol-3-yl S-butyl phosphorothioate: 0- (6, 7, 8-trimethylxanthene-9-thione-4-yl) S-ethyl S-butyl phosphor Dithiolate: 0-ethyl 0- (4-trifluoro-methylxanthene--9-thione-2-yl) S-propyl phosphorothiolothionate: 0-ethyl 0- (6-ethylsulfonyl Santen-9-thion-1-yl) S-propyl phosphorothioolothionate: 0- (8-propylsulfinylxanthene-9-thion-2-yl) 6, S-dipropyl phosphorodithiothiothioneate : 0-ethyl 0-xanthen-9-one-2-yl) S-propyl phosphorothiolothionate: 0-pentyl0- (2-ethyl-6-chloroxanthene-9-one-1-yl ) S-propyl phosphorothioolothionate: 0-ethyl 0- (5-chloroxanthene-9-ten-9-one-2-yl) N, N-dimethyl phosphoramidate: 0- (6- Methylxanthene-9-one-2-yl) S-butyl N, N-dipentyl phosphoramidothiolate: 0- (8-ethylsulfinylxanthene-9-one-2-yl) S-hexyl S -Propyl phosphoramidothiolate: 0- ( 2-butylxanthene-9-one-2-yl) S-propyl phosphoraminothiolothionate and the like.

Indeed, when used as a pesticide, the compounds of the present invention are consistent with pesticidal compounds containing such compounds in an inert carrier and a pesticidal toxicity. Insecticidal compositions, so-called preparations, are active compounds that can be used simply on the insect's periphery at any viewing dose.

These compositions may be solid, such as powdered granules or hydrating agents, or may be liquids such as solutions, erosols or emulsifiable concentrates. For example, powder may be prepared by decomposing and mixing the active compound with a solid inert carrier such as talc, clay, silica, pyrophyllite, and the like. Granules can be prepared by immersing in and in granule carriers, such as attapulgite or vermiculite, usually in the range of about 0.3 to 1.5 mm, dissolved in a suitable solvent.

Wetting agents, which can be dispersed in water and / or oil of any desired concentration of active compound, can be prepared by incorporating a humectant into the concentrated powder composition. In some cases, the active compound can be used directly as a solution in such a solvent because it is sufficiently soluble in conventional organic solvents such as kerosene or xylene. Pesticide solutions can often be dispersed as aerosols under superatmospheric pressure.

However, preferred liquid insecticide compositions are emulsifiable concentrates, which are active compounds according to the invention and contain solvents and emulsifiers as inert carriers. Such emulsifiable concentrates can be diluted with water or flow paths at any desired concentration of the active compounds of the present invention such that spraying can be used at the site of impact.

The most commonly used emulsifiers in such concentrates are nonionic surfactants or mixtures of anionic and nonionic surfactants. Typical pesticide compositions according to the invention are described in the following examples, where the amount is parts by weight.

Example 19

The manufacture of dust

Product 10 of Example 1

Powder Talc 90

The components are mixed in a milling mixer and ground until a homogeneous fluidized bed agent of the desired particle size is obtained.

This powder is suitable for use directly on the affected area. The compounds according to the invention can be used as pesticides by any method recognized in the art.

One of the methods of exterminating pests is to use the compound of the invention in toxic amounts, to use pesticidal compositions containing inert carriers or as essential active ingredients. In pesticidal compositions the concentration of novel compounds according to the invention varies widely depending on the form of the formulation and the intended purpose, but generally the pesticide composition contains from about 0.05 to about 95% by weight of the active compound of the invention. In a preferred embodiment of the invention the pesticidal composition contains about 5 to 75% by weight of active compound.

The composition may also contain additional substances such as pesticides, safety agents, electrodeposition agents, deactivators, tackifiers, fixing agents, fertilizers, active agents, auxiliaries and the like.

The compounds of the present invention are also useful when mixed with other pesticides in the pesticide compositions described above. These other pesticides may contain about 5 to 95% of the active ingredient in the pesticide composition.

The use of the compounds of the present invention in combination with other pesticides provides pesticide compositions that are more effective in inhibiting pests and often provide unachievable results with separate insecticide compositions. Compounds of the invention and other pesticides that can be used as pesticide compositions to control pests include DDT, methcyclocyclo, TDE, lindane, chlordan, isobenzene, aldrin, dieldrin, heptachloro, andrin, mirex Halogenated compounds such as, endosulfone, dicopol, etc .: TEPP, Spradan, Aerion, Parathion, Methyl Parathion, PEN, Demethone, Carbophenothione Forate, Ginopox, Diazinon, Malathion, Melvin Force, Dimetho Organophosphorus compounds such as Eight, DBD, Ronnel, Oxydimethone-methyl, Dicamtone, Chlorothione, Phospamidon, Naled, Pention, Trichlorophone, DDVP, etc .: dinitro-0-cresol, dinitrocyclohexyl Organic nitrogen compounds such as phenol, DNB, DNP, vinacrylazobenzene, etc .: organic carbamate compounds such as carbaryl, ortho 5353 and the like: phenothiazine, phenoxatine, lauryl thiocyannetbis (2-thiosi Anoethyl) ether Organic sulfur compounds such as isobornylthiocyanoacetate, etc. Hydrogen cyanide, carbon tetrachloride, calcium cyanide, carbon disulfide, ethylene, dichloride, propylene, dichloride ethylene dibromide, ethylene oxide, methyl bromide, paradichlorobenzene, etc. It may contain the same material.

The compounds of the present invention may also be mixed with strains and fungicide nematode compounds which in some cases produce pesticides useful for soil nematodes and pest control. Representative examples of such bactericidal compounds are ferbam, nabam, janeb, tiram, ziram, chloranil, diclones, gliodine, cycloheximide, dinokal, maneb, captan, dodine, PCNB, P-dimethylamino benzenedia Josodium sulfonate, etc., Examples of nematicide compounds include chloropicrine 0, 0-diethyl 0- (2,4-dichlorophenyl) phosphorothioate, tetra chlorothiophene, dazometh, dibrochloropan and the like. There is this.

The novel compounds according to the invention can be used in various ways to control pests.

Insecticides used as internal poisoning or protective substances may be used on surfaces where pests reproduce and migrate. Insecticides used as contact poisons or exterminators can be used directly on the body of pests by residue treatment on the surface where the pest walks or crawls, or by fumigation of the air the pest breathes.

In some cases, plants absorb this compound for use on soil or plant surfaces, and pests are poisoned throughout the body. The method of using pesticides is based on the fact that all the common injuries suffered by pests are the direct or indirect consequences of the pest's attempt to obtain food.

및 사과구더기와 같은 것 또한 사과잎마이너(miner) 자작나무잎마이너, 사탕나무잎마이너, 와 같은 잎마이너, 밀마디충, 포도뿌리 혹 벌레와 같은 내부에서 먹은 해충이 있다. 땅표면 아래에서 공경하는 해충은 땅속 해충으로 분류되고 또한 털이덮인 사과진딧물, 일본딱정벌레, 양파구더기와 옥수수 뿌리벌레와 같은 파괴적 충해가 포함된다.Indeed, a number of destructive pests are broadly classified based on their diet. Among the pests effectively inhibited by the present invention are chewing pests such as Mexican bean beetles and southern moth moths: pea aphids, grain leaf beetles, housefly, stag beetle, peanut bugs, lygus bugs, oyster bark bees, California red Cicada-like pests such as rain, Florida red rain, fuel economy and soft mosquitoes. Parasites, plum weevil, red stripe, melon beetle, cabbage looper

And apple maggots also have internal insects such as apple leaf minor (miner) birch leaf minor, cane leaf minor, leaf minor such as wheat grasshopper, grape root beetle and insects. Pests honoring below the surface of the earth are classified as underground pests and also include destructive insects such as hairy apple aphids, Japanese beetles, onion maggots and corn root beetles.

The amount of active compound of the present invention used for pest control depends on the change of factors such as the particular pest to be targeted, the sensitization intensity, the climate, the form of the environment, the formulation type and the like.

For example, using only one or two ounces of active compound per acre requires about one pound or more of active compound per acre to suppress severe infection by pests under conditions desirable for the development of the pest, It would be suitable to suppress mild infection by pests under undesirable conditions.

The pesticidal action of the compounds according to the invention has been demonstrated in experiments conducted on the inhibition of various pests. The desired amount of test compound (determined by the concentration or rate of use to be used in additional tests) is dissolved in acetone solvent containing 3.19 g of Triton X-155R (alkylarylpolyetheralcohol) per liter. Or disperse.

When dissolved or dispersed in acetone, 4 parts by weight of acetone solution or spray is diluted with 96 parts by weight of distilled water. If the test compound is insoluble in acetone or distilled water, it is dispersed using a paper mill.) A low concentration test solution is 4 parts by weight of acetone containing 3.19 g of Triton X 155R per 96 parts of distilled water and 4 parts by weight of 1 L. It can be prepared in high concentration solution dilution with dilution.

Plants to be used in these experiments are prepared by planting seeds suitable for sterile soil housed in plastic test pots (square test pieces with 3.5-inch sides) with an upper soil surface area of approximately 12.25 square inches. After sowing the seeds, a layer of 0.25 inches of sand is usually sprayed on the surface of the soil. The test compound is used after the plant has reached a certain size. For foliar use, the test compound is dissolved or dispersed in the solvent of water and acetone described above and sprayed on the foliage of the test plant as fog.

The concentration of the test compound and the total amount of solution to be used are adjusted to the desired concentration or rate, and the plants are then air dried. The solution and aphid are exposed to the treated leaves attached to the plant. Other pests are exposed to the treated leaves removed from the plants.

Place 1 wet filter paper in a Petri dish. For soil immersion use, the test compound is first dissolved or dispersed in water and acetone as described above, and then the pipette is evenly sprayed onto the soil surface in the test powder in the amount required to determine the desired rate of use.

Within 24 hours after this treatment, mites and aphids are exposed to the leaves remaining in the treated plants. Other pests are exposed to the leaves removed from the plants 24 hours after treatment. Then place it on a glass dish containing a sheet of wet filter paper. In direct contact use, the test compound is also first formulated in acetone solution with water at the concentration to be tested as described above. The pest to be tested is then added.

Spray pesticides and also immerse in liquid and dry to observe the results. In the experimental data indicated below as PPM (million 1), the test drug was sprayed on the plants directly or by foliar spraying. In this experiment, the use rate is expressed as # / A (lbs per acre) and the test agent is used as the soil submersion. Inhibition rate is the mortality rate of the pests tested.

Cabbage bug

The bushy variety 222 of the TWO-Leaf Stage (Burpee Variety 222) is exposed to the test compound in two different ways, using foliar spraying and soil soaking techniques.

The leaves are removed from the plants for about 30 minutes by air application using foliar spraying and after 24 hours using soil soaking, and then placed in a petri dish containing a sheet of wet filter paper. Place on each petricia and cover the plate. Pest killings are performed 48 hours after exposure.

The test results are shown in detail in the following table.

[Table 1]

Suppression rate

Note: (1) Average of 2 tests

(2) surviving insects whose growth is inhibited

Southern Great Antarctic Moth

Two-leafed shrub variety 222 (Burpee Variety 222) is exposed to the test compound using two techniques, foliar spraying and soil immersion, at varying rates of use. The leaves are removed from the plants after about 30 minutes of air drying with foliar spraying and after 24 hours with soil soaking, and placed in a petri dish containing one wet filter paper.

Ten South Great Antarctic Moths of the Second Larvae are placed in each Petri Dish. Pest mortality is measured 48 hours after exposure. The results of this test are detailed in the second table below.

[Table 2]

Suppression rate

Note: (1) Average of 2 tests

(2) surviving insects whose growth is inhibited

Locust beetle

Two-leafed shrub variety 222 (Burpee Variety 222) is exposed to the test compound at two different rates, using foliar spraying and soil immersion.

The leaves, after about 30 minutes of air drying for foliar spraying and after 24 hours for soil immersion, are removed from the plant and placed in a petri dish containing a single wet filter paper and covered with a plate. Pest mortality is measured 48 hours after exposure.

The results of this test are detailed in Table 3 below.

[Table 3]

Suppression rate

Note: (1) Average of 2 tests

(2) surviving insects whose growth is inhibited

Cigarette eye bug

Burping variety 222 of the bud stage (Burpee Variety 222) is exposed to the test compound by two techniques, foliar spraying and soil immersion, at varying rates of use.

The leaves are removed from the plant after about 30 minutes of air drying with foliar spraying and after 24 hours with soil soaking and placed in a petri dish containing a piece of wet filter paper.

Ten larvae of the second larvae are placed in petri dishes and the dishes are covered. Pest mortality is measured 48 hours after exposure.

The test results are detailed in Table 4 below.

[Table 4]

Suppression rate

Note: (1) Average of 2 tests

(2) surviving insects whose growth is inhibited

Mesikacan Bean Beetle

Bud variety 222 (Burpee Variety 222) is exposed to the test compound by two techniques, foliar spraying and soil immersion, with varying utilization rates.

The leaves are detached from the plant after about 30 minutes of air drying for foliar spraying and after 24 hours for soil soaking, and then placed in a petri dish containing a single wet filter paper to cover the dish. Pest mortality is measured 48 hours after exposure.

The results of this test are shown in Table 5 below.

[Table 5]

Tara weevil

Sprout-stage cotton plants (Deltapine 16) are exposed to the test compound in two different techniques, foliar spraying and soil immersion. After about 30 minutes of air drying for foliar spraying and after 24 hours for soil immersion, the leaves are removed from the plant and placed in a Petri dish containing a sheet of wet filter paper to cover the dish. Pest mortality is measured 48 hours after exposure.

The results of the test are shown in detail in Table 6 below.

[Table 6]

Suppression rate

Pea

Peas plants 10-14 days old are treated with the test compound in two different ways, with foliar spray and soil immersion.

This plant is reagentd as a foliar spray and then air dried for about 30 minutes, and then 25-50 adult and nymph pea aphids are applied to the treated plants and untreated controls, respectively, with a small paintbrush. The plants are infected with 25 to 50 aphids using the techniques described above 24 hours after the plants have been treated with the soil immersion method.

Infect untreated plants equally. After 48 hours of exposure to the treated plants, the pest mortality is measured by comparing the number of pests of the treated plants with that of the untreated control plants.

The test results are shown in Table 7 below.

[Table 7]

Suppression rate

Head spot solution

Burpee Variety at the bud stage is treated with the test compound in two ways: foliar spray and soil immersion at various rates of use.

Reagent this plant with foliar spray and air dry for about 30 minutes. Two spot mites of 50 to 100 adults and nymphs are then placed in the treated and untreated plants, respectively, and 50 to 100 untreated infected soybean leaves are placed in the plants. After the plants have been treated with soil immersion, the plants are infected with 50 to 10 mites using the technique described above 24 and a half hours later. Infect uncontrolled plants equally.

After 48 hours of pest exposure to the treated plants, the pest mortality is measured by comparing the pest number of the treated plants with that of the untreated control plants.

The test results are shown in Table 8 below.

[Table 8]

Suppression rate

housefly

10 grown flies are placed in a wire mesh glass with a small (2 "-3") plastic lid. We spread the test compound to the desired concentration in the solution prepared as described above.

After spraying, the treated cages are stored until dry. 60 minutes after spraying, the fly is exhausted. Then we place it on a paper towel moistened with 5-10% sucrose solution. The paper towel is stored for 23 hours and the mortality rate is measured for 24 hours after treatment.

The test results are shown in Table 9 below.

[Table 9]

Suppression rate

Suppression rate

Attention: k = 60 minutes

mortality rate after m = 24 hours

German wheel

Prepare a test compound solution as described above and place this solution in the flask at the desired concentration. Ten adult German wheels are placed in a tea strainer and immersed in the test solution.

The excess solution is removed, the tea strainer net is opened and the pests are placed in a transparent plastic container containing another small wet dental case.

The container is then covered with a lid and air holes are drilled through the lid. Pest mortality is observed 48 hours after exposure.

The test results are shown in Table 10 below.

[Table 10]

Suppression rate

Southern Corn Roots

Freshly germinated corn seeds are placed in a 1-ounce plastic cup with a snap-on plastic lid and covered with approximately 5 g of sterile soil.

As described above, the test compound is treated with the soil by the soil immersion method at the desired rate of use. After treatment, the lid is left open on the cup and the cup is left to stand for about 15 minutes to spread evenly over the soil. The lid is removed, five rootworm larvae larvae are placed on the treated soil and the cup is closed again.

The cup is checked to detect pest mortality after 72 exposures. Larvae that cannot crawl or are intact are considered dead.

The results of this test are shown in Table 11 below.

[Table 11]

Suppression rate

Yellow heat mosquito

A solution containing the test compound at the desired concentration is prepared as described above.

Each test solution is placed in a 10 oz. Capacity foamed polystyrene cup. About 10 to 4 days old yellow fever larvae are placed in each test solution using an eye dropper.

To each test solution is added a small amount of brewer's yeast and an extremely small piece of dried food (a broken solid dog food). Mortality data is confirmed 48 hours after exposure.

This data is shown in Table 12 below.

[Table 12]

Suppression rate

Claims (1)

A process for preparing the following compound of formula (I), wherein the compound of formula (II) is reacted with the compound of formula (III).

In the above formulas, R ¹ and R ² are each selected from the group consisting of lower alkyl and cyano; k and m are 0 to 1; Q and Y are selected from the group consisting of oxygen and sulfur; R ³ is lower alkyl and structural formula

Wherein R ⁵ is selected from the group consisting of halogen, lower alkyl and cyano, and n is from 0 to 3); R ⁴ is alkyl, lower alkoxy and structural formula

Wherein R ⁶ is selected from the group consisting of lower haloalkyl, nitro and cyano; and P is 0-3, and A and B are each composed of oxygen and sulfur It is selected from a group. Provided that when R ⁴ is lower alkoxy one of A and B must be sulfur.